US2755291A - Certain quaternary ammonium azides - Google Patents
Certain quaternary ammonium azides Download PDFInfo
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- US2755291A US2755291A US461018A US46101854A US2755291A US 2755291 A US2755291 A US 2755291A US 461018 A US461018 A US 461018A US 46101854 A US46101854 A US 46101854A US 2755291 A US2755291 A US 2755291A
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- Prior art keywords
- choline
- quaternary ammonium
- azide
- azides
- aqueous
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C247/00—Compounds containing azido groups
Definitions
- R, R1 and R2 are lower alkyl groups having from one to three carbon atoms
- R3 is a divalent aliphatic hydrocarbon radical having one to four carbon atoms.
- Another object of this invention is the preparation of hypotensive agents which are effective at low dosage levels and which may be administered both orally and intravenously.
- quaternary ammonium hydroxide compounds which may be reacted with HNs to form said novel azides, there may be mentioned compounds such as trimethylhydroxyethyl-ammonium hydroxide, also known as choline, trimethylhydroxypropyl-ammonium hydrox de, trimethyl-( ,B-methyl) hydroxyethyl-ammonium hydroxlde, also known as fi-methyl choline, and trimethylhydroxybutyl-ammonium hydroxide.
- Example I 3.8 parts by weight of sodium azide are placed in a reaction vessel and 18 parts by weight of concentrated sulfuric acid slowly added to generate hydrazoic acid, HNs.
- the hydrazoic acid formed is passed through 16.7 parts by weight of an aqueous solution containing 48% by weight of the bicarbonate of trimethylhydroxyethylammonium hydroxide, i. e. choline, with the aid of a stream of nitrogen.
- the resulting aqueous solution obtained after completing the reaction comprises a 35% by weight aqueous solution of choline azide.
- Example 11 0.2 mol of choline chloride (other choline salts, such as choline citrate, may be used) is dissolved in ml- Water. To this solution the basic form of IRA-400 Amberlite resin is added until a pH of 11.9 is reached. A. small excess of resin is then further added, and the mix-- ture is filtered immediately to remove the resin. Freehydrazoic acid (prepared from sodium azide and sulfuric acid) is then bubbled into the aqueous solution of free: choline base until a pH of 7.5 is reached. The water is: removed under vacuo leaving an oily residue of choline azide.
- choline chloride other choline salts, such as choline citrate, may be used
- R, R1 and R2 are lower alkyl groups having one to three carbon atoms, and R3 is a divalent aliphatic hydrocarbon radical having one to four carbon atoms 2.
- R, R1 and R2 are lower alkyl groups having one to three carbon atoms
- R3 is a divalent aliphatic hydrocarbon radical having one to four carbon atoms, which comprises reacting said quaternary ammonium hydroxide compound with hydrazoic acid.
- Process for the preparation of choline azide which comprises reacting choline with hydrazoic acid in an aqueous medium and separating the choline azide formed by evaporating the aqueous solvent.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
United States Patent CERTAIN QUATERNARY AMMONIUM AZIDES Robert H. Broh-Kahn, Hastings-on-Hudson, Theodore I. Fand, White Plains, and Leon E. Tenenbaum, Ardsley, N. Y., assignors to Nepera Chemical Co., Inc., Yonkers, N. Y., a corporation of New York No Drawing. Application October 7, 1954, Serial No. 461,018
8 Claims. (Cl. 260349) This invention relates to certain novel azides, and relates more particularly to the azides, or hydrazoic acid salts, of quaternary ammonium compounds of the following formula:
wherein R, R1 and R2 are lower alkyl groups having from one to three carbon atoms, and R3 is a divalent aliphatic hydrocarbon radical having one to four carbon atoms. These compounds are valuable hypotensive agents and are effective in producing a pronounced and prolonged drop in blood pressure either by intravenous or oral administration.
An object of this invention is the preparation of certain novel organic salts of hydrazoic acid which are useful as hypotensive agents.
Another object of this invention is the preparation of hypotensive agents which are effective at low dosage levels and which may be administered both orally and intravenously.
Other objects of this invention will appear from the following detailed description.
We have found that by reacting hydrazoic acid, HNa, with a quarternary ammonium hydroxide of the formula wherein R, R1 and R2 are lower alkyl groups having from one to three carbon atoms, i. e. a methyl, ethyl or propyl group; R3 is a divalent aliphatic hydrocarbon radical having one to four carbon atoms, and R4 is hydrogen, or a methyl, ethyl, or propyl group, the hydroxy group on the pentavalent nitrogen is replaced by an azide group and hydrazoic acid salts having valuable hypotenswe activity are obtained.
As examples of quaternary ammonium hydroxide compounds which may be reacted with HNs to form said novel azides, there may be mentioned compounds such as trimethylhydroxyethyl-ammonium hydroxide, also known as choline, trimethylhydroxypropyl-ammonium hydrox de, trimethyl-( ,B-methyl) hydroxyethyl-ammonium hydroxlde, also known as fi-methyl choline, and trimethylhydroxybutyl-ammonium hydroxide.
The reaction of said quaternary ammonium hydroxide bases with hydrazoic acid may be carried out conveniently by passing vapors of hydrazoic acid through an aqueous solution of the free base. Further, the same reaction may be brought about by the addition of an aqueous or alcoholic solution of HNs to an aqueous or alcohohc solu- "ice tion of quaternary base in stoichiometric quantities. .An aqueous or alcoholic solution of the salts of the free base such as the bicarbonate, bisulfite or any weak, displaceable acid may also be utilized. The reaction is readily etfected at temperatures of 20 C. to 50 C.
In order further to illustrate my invention but without being limited thereto, the following examples are given:
Example I 3.8 parts by weight of sodium azide are placed in a reaction vessel and 18 parts by weight of concentrated sulfuric acid slowly added to generate hydrazoic acid, HNs. The hydrazoic acid formed is passed through 16.7 parts by weight of an aqueous solution containing 48% by weight of the bicarbonate of trimethylhydroxyethylammonium hydroxide, i. e. choline, with the aid of a stream of nitrogen. The resulting aqueous solution obtained after completing the reaction comprises a 35% by weight aqueous solution of choline azide.
Example 11 0.2 mol of choline chloride (other choline salts, such as choline citrate, may be used) is dissolved in ml- Water. To this solution the basic form of IRA-400 Amberlite resin is added until a pH of 11.9 is reached. A. small excess of resin is then further added, and the mix-- ture is filtered immediately to remove the resin. Freehydrazoic acid (prepared from sodium azide and sulfuric acid) is then bubbled into the aqueous solution of free: choline base until a pH of 7.5 is reached. The water is: removed under vacuo leaving an oily residue of choline azide.
An alternative procedure for preparing choline azidecomprises reacting choline chloride or other choline salt with a metal azide such as sodium azide in methanol 01'' other suitable solvent in which the reactants are solubleand the metal salts formed are substantially insoluble. The sodium chloride formed as a byproduct precipitates from solution and may be filtered ofi. On evaporation of the solvent, choline azide is obtained as an oily residue.
It is understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of our invention.
What we claim is:
l. Azides of the following formula:
wherein R, R1 and R2 are lower alkyl groups having one to three carbon atoms, and R3 is a divalent aliphatic hydrocarbon radical having one to four carbon atoms 2. The azide of the formula:
CH3 I la 3. Process for the preparation of quaternary ammonium azides of hydroxide compounds of the formula:
wherein R, R1 and R2 are lower alkyl groups having one to three carbon atoms, and R3 is a divalent aliphatic hydrocarbon radical having one to four carbon atoms, which comprises reacting said quaternary ammonium hydroxide compound with hydrazoic acid.
4. Process in accordance with claim 3 wherein said reaction is carried out in an aqueous reaction medium.
5. Process in accordance with claim 3 wherein said reaction is carried out in an aqueous reaction medium and the azide separated by evaporating the aqueous solvent.
6. Process for the preparation of choline azide, which comprises reacting choline with hydrazoic acid.
7. Process for the preparation of choline azide, which comprises reacting choline with hydrazoic acid in an aqueous medium.
8. Process for the preparation of choline azide, which comprises reacting choline with hydrazoic acid in an aqueous medium and separating the choline azide formed by evaporating the aqueous solvent.
No references cited.
Claims (1)
1. AZIDES OF THE FOLLOWING FORMULA:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US461018A US2755291A (en) | 1954-10-07 | 1954-10-07 | Certain quaternary ammonium azides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US461018A US2755291A (en) | 1954-10-07 | 1954-10-07 | Certain quaternary ammonium azides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2755291A true US2755291A (en) | 1956-07-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US461018A Expired - Lifetime US2755291A (en) | 1954-10-07 | 1954-10-07 | Certain quaternary ammonium azides |
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| Country | Link |
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| US (1) | US2755291A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3236789A (en) * | 1962-02-06 | 1966-02-22 | Du Pont | Process for making foamed polycaprolactam |
| US3309439A (en) * | 1964-11-06 | 1967-03-14 | Lakeside Plastics Corp | Method of producing an expanded polystyrene foam having a dense surface |
-
1954
- 1954-10-07 US US461018A patent/US2755291A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3236789A (en) * | 1962-02-06 | 1966-02-22 | Du Pont | Process for making foamed polycaprolactam |
| US3309439A (en) * | 1964-11-06 | 1967-03-14 | Lakeside Plastics Corp | Method of producing an expanded polystyrene foam having a dense surface |
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